CHNS/O Determination in Coals Using

Ap plica t ion Note 4221 8

the Thermo Scientific FLASH 2000
Elemental Analyzer
Dr. Liliana Krotz, OEA Product Specialist, Dr. Francesco Leone, OEA Application Specialist,
and Dr. Guido Giazzi, OEA Product Manager
Thermo Fisher Scientific, Milan, Italy

Key Words
Coal, CHNS/O, Elemental Analysis, CO2 Emission Trade, Heat Value

Goal
This application note reports Nitrogen, Carbon, Hydrogen, Sulfur
and Oxygen data in coal samples, the relative Heat Values and CO2
Emission Trade Evaluation

Introduction
Coal is the largest source of energy worldwide but it is
also considered as a source of pollution since various
toxic chemicals are released in the environment as
by-products during the coking process. Environmental
pollutants such as sulfur dioxide, sulfuric acid and
hydrogen sulfide are related to sulfur concentration on As the demand for improved sample throughput,
coal. The composition of coal varies depending on the reduction of operational costs and minimization of human
place where it formed and which kind of soil or rock errors increases, a simple and automated technique which
determined its formation. This means that its composition allows fast analysis with an excellent reproducibility is the
and properties affect its final use and its impact on key for efficient elemental analysis. The Thermo
the environment. Scientific™ FLASH™ 2000 CHNS/O Analyzer (Figure 1)
enables the fast quantitative determination of the elements
Given environmental concerns and forthcoming
in large concentrations with no need for sample digestion
legislation the elemental analysis of coal is important
providing important advantages in terms of time and
for its quality control. In particular sulfur quantification
automation. The system, which operates with dynamic
helps identify pollutants. The method for CHN
combustion of the sample, provides automated and
determination is described in ASTM D5373-02 Method.
simultaneous CHNS determination in a single analysis run
The method covers the analytical determination of
and it provides oxygen determination by pyrolysis in a
nitrogen, carbon and hydrogen in coal and coke samples.
consequent run. From the CHNS/O data obtained, the
dedicated Thermo Scientific™ Eager Xperience Data
Handling Software calculates the heat value GHV and
NHV (Gross Heat Value and Net Heat Value, both
expressed in kcal/kg) and the CO2 Emission Trade data.

Figure 1. Thermo Scientific FLASH 2000 CHNS/O Analyzer.

2 Methods
For the CHNS determination, the FLASH 2000
Analyzer operates with the dynamic flash combustion
of the sample. Samples are weighed in tin containers and
introduced into the combustion reactor via the Thermo
Scientific™ MAS™ 200R Autosampler with the proper
amount of oxygen. After the combustion the analyte gases
are carried in a helium flow to a layer containing copper,
then swept through a GC column which provides the
separation of the combustion gases and finally, they are
detected by a Thermal Conductivity Detector (TCD).
Total run time is 10 minutes (Figure 2).
For the determination of oxygen, the system operates
in pyrolysis mode. Samples are weighed in silver
capsules and introduced into the pyrolysis chamber
via the MAS 200R Autosampler. The reactor contains
nickel coated carbon at a temperature of 1060 °C.
When the oxygen in the sample is combined with
carbon, it forms carbon monoxide which is then
chromatographically separated from other products
and detected by the TCD detector (Figure 2). A report
is generated by the Eager Xperience Data Handling
Software and it is displayed at the end of the analysis.
Results
Different coal samples were analyzed to demonstrate the
reproducibility in the FLASH 2000 Analyzer. Samples
were homogenized by a ball mill.
Table 1 shows the CHNS data of six coal samples,
which were analyzed ten times consequently. Instrument
calibration was performed with 2–3 mg of BBOT (2,5-Bis
(5-ter-butyl-benzoxazol-2-yl) thiophene) OEA Standard.
No matrix effect was observed when changing the sample.
Figure 3 shows a typical CHNS chromatogram.

CHNS Configuration Oxygen Configuration

Autosampler Autosampler

Oxygen Helium Helium

Pyrolysis

Oxidation GC Column
H2O Trap

Reduction
TCD

GC Column Eager Xperience

Figure 2. FLASH 2000 CHNS/O determination layout.

Figure 3. Typical CHNS chromatogram.

Table 1. CHNS Repeatability of 10 determinations of coal samples. 3

Sample A B
Element N% C% H% S% N% C% H% S%
1.93 88.48 3.76 4.16 1.15 81.54 4.18 0.41
1.95 88.51 3.76 4.19 1.15 82.45 4.17 0.41
1.94 88.34 3.76 4.21 1.14 82.53 4.17 0.41
1.93 88.21 3.75 4.20 1.14 82.36 4.17 0.40
1.93 87.95 3.74 4.21 1.13 81.99 4.17 0.41
1.95 88.49 3.75 4.20 1.14 82.14 4.16 0.40
1.93 88.21 3.74 4.20 1.13 81.86 4.16 0.40
1.94 88.45 3.75 4.21 1.14 82.60 4.18 0.40
1.94 88.46 3.76 4.21 1.13 81.59 4.14 0.41
1.94 88.04 3.73 4.18 1.14 82.02 4.16 0.41
Mean % 1.94 88.31 3.75 4.20 1.14 82.11 4.17 0.41
RSD % 0.41 0.23 0.28 0.39 0.65 0.46 0.28 1.27

Sample C D
Element N% C% H% S% N% C% H% S%
1.00 79.31 4.34 0.31 1.75 77.77 4.27 0.54
1.00 79.85 4.37 0.32 1.76 78.14 4.25 0.53
1.01 80.31 4.40 0.32 1.75 78.24 4.26 0.54
1.00 79.98 4.38 0.31 1.75 77.95 4.23 0.52
1.00 79.41 4.34 0.31 1.75 77.94 4.23 0.52
1.01 80.07 4.38 0.30 1.75 77.91 4.24 0.54
1.01 79.88 4.38 0.32 1.75 77.76 4.23 0.52
1.01 79.56 4.37 0.31 1.75 77.90 4.24 0.54
1.01 79.82 4.36 0.31 1.76 78.23 4.24 0.53
1.02 80.16 4.40 0.30 1.77 78.64 4.26 0.53
Mean % 1.01 79.83 4.37 0.31 1.75 78.05 4.24 0.53
RSD % 0.67 0.40 0.48 2.37 0.40 0.34 0.34 1.65

Sample E F
Element N% C% H% S% N% C% H% S%
0.81 65.85 4.43 0.18 1.14 79.71 4.30 0.28
0.81 65.85 4.48 0.17 1.14 78.98 4.22 0.27
0.82 65.65 4.40 0.18 1.14 79.48 4.25 0.28
0.81 65.80 4.41 0.18 1.14 79.83 4.26 0.28
0.82 65.96 4.46 0.16 1.14 79.54 4.24 0.27
0.83 66.18 4.40 0.17 1.15 79.53 4.24 0.27
0.82 65.81 4.47 0.17 1.15 79.63 4.24 0.28
0.82 65.45 4.41 0.18 1.14 79.40 4.23 0.28
0.81 65.53 4.39 0.16 1.15 80.07 4.27 0.27
0.81 65.01 4.40 0.16 1.15 79.64 4.26 0.28
Mean % 0.82 65.71 4.42 0.17 1.14 79.58 4.25 0.28
RSD % 0.86 0.49 0.75 5.12 0.45 0.36 0.54 1.87
4 Table 2 shows the oxygen data from the coal samples. The Value and Net Heat Value expressed in kcal/kg) and the
calibration was performed with 1–2 mg of BBOT (2,5-Bis CO2 Emission Trade, which are automatically calculated
(5-tert-butyl-benzoxazol-2-yl) thiophene). Table 3 reports by the Eager Xperience Data Handling Software. Figure 4
the heat value GHV and NHV (Gross Heat shows a typical chromatogram of Oxygen determination.

Table 2. Oxygen determination of coal samples in triplicate.

Sample A B C D E F
1.10 3.42 5.36 3.83 14.84 4.28
Oxygen % 1.11 3.44 5.36 3.77 14.85 4.28
1.09 3.43 5.34 3.80 14.94 4.26
Av. Oxygen % 1.10 3.43 5.35 3.80 14.88 4.27
RSD % 0.91 0.29 0.22 0.79 0.37 0.27

Table 3. Heat Value and CO2 Emission Trade calculation of coal samples.

Sample A B C D E F
GHV (kcal/kg) 8589 8030 7827 7709 6273 7810
NHV (kcal/kg) 8397 7816 7602 7491 6047 7592
CO2 E.T. 92.07 91.97 91.93 91.22 95.14 91.76

Figure 4. Typical chromatogram of Oxygen determination.

The performance of the FLASH 2000 Analyzer was Table 4. Concentration Range and Limit of Repeatability* accepted by
validated by comparing the repeatability of the CHN ASTM D 5373-02.
data with the ASTM D 5373-02 requirements, showed
Concentration Range Repeatability Limit
in Table 4. Element
(%) (r)
Carbon 48.6 to 90.6 0.64
Hydrogen 0.14 to 5.16 0.16
Nitrogen 0.69 to 1.57 0.11

* Repeatability Limit (r): the value below which, the absolute

difference between two test results calculated to a dry basis of
separate and consecutive test determinations, carried out on the
same sample, in the same laboratory, by the same operator, using
the same apparatus.
The precision of the FLASH 2000 for CHN determination and the difference (Diff.) calculated between both data.
was demonstrated by performing three series of analysis All differences are acceptable and they are less than the

Ap plica t ion Note 4221 8

of the six Coal samples, which were analyzed twice. The Repeatability Limit, which is indicated in the Official
calibration of the system was performed with 2–3 mg of method, meaning a good homogeneity and the total
acetanilide. Coal sample A weighed 2–2.5 mg and coal combustion of the samples.
samples B-F 2.5–3 mg. Table 5 shows the CHN results

Table 5. CHN data of coal samples in duplicate using CHN reactor.

Series Elem Coal Samples

A B C D E F
% Diff. % Diff. % Diff. % Diff. % Diff. % Diff.
88.36 82.58 80.04 78.34 65.82 79.93
1 C 0.08 0.04 0.38 0.27 0.02 0.06
88.44 82.54 79.66 78.61 65.80 79.87
3.72 4.24 4.45 4.36 4.60 4.30
H 0.02 0.04 0.07 0.05 0.13 0.02
3.74 4.20 4.38 4.31 4.47 4.28
1.88 1.17 1.01 1.71 0.80 1.15
N 0.02 0.03 0.02 0.03 0.00 0.04
1.90 1.14 0.99 1.74 0.80 1.11
88.04 82.25 79.46 77.82 66.20 80.09
2 C 0.09 0.19 0.30 0.56 0.17 0.09
87.95 82.06 79.73 78.38 66.03 80.18
3.75 4.19 4.38 4.27 4.45 4.28
H 0.02 0.01 0.00 0.03 0.04 0.02
3.73 4.18 4.38 4.30 4.41 4.30
1.88 1.13 0.98 1.71 0.80 1.15
N 0.00 0.02 0.01 0.03 0.00 0.00
1.88 1.11 0.99 1.74 0.80 1.15
88.28 82.35 80.06 77.96 65.94 80.10
3 C 0.24 0.02 0.45 0.50 0.07 0.09
88.04 82.37 79.61 78.46 66.01 80.01
3.74 4.20 4.44 4.27 4.49 4.29
H 0.02 0.01 0.06 0.03 0.01 0.02
3.72 4.19 4.38 4.30 4.48 4.27
1.83 1.14 1.00 1.71 0.80 1.18
N 0.02 0.00 0.01 0.03 0.00 0.01
1.85 1.14 0.99 1.74 0.80 1.17

Conclusion No matrix effect was observed when changing the sample,

The Thermo Scientific FLASH 2000 Analyzer proved to meaning that samples were entirely combusted.
be a valuable solution for the analysis of CHNS/O in
The Thermo Scientific FLASH 2000 Analyzer allows
coal samples in terms of accuracy, reproducibility and
CHNS and oxygen determinations (by changing
sensitivity. Its automation, high speed of analysis and
configuration), removing the need for any extra modules,
the elimination of sample preparation processes allow
reducing operational cost, while increasing speed
efficient analysis and reduce overall operational costs.
per analysis.
All data showed good repeatability and met the
requirements of the ASTM D 5373-02 Method.

www.thermoscientific.com
©2015 Thermo Fisher Scientific Inc. All rights reserved. ISO is a trademark of the International Standards Organization.
ASTM is a trademark of the American Society for Testing and Materials. All other trademarks are the property of Thermo
Fisher Scientific and its subsidiaries. This information is presented as an example of the capabilities of Thermo Fisher
Scientific products. It is not intended to encourage use of these products in any manners that might infringe the intellectual
property rights of others. Specifications, terms and pricing are subject to change. Not all products are available in all Thermo Fisher Scientific S.p.A. Milan, Italy
countries. Please consult your local sales representative for details. is ISO 9001:2008 Certified.

Africa +43 1 333 50 34 0 Denmark +45 70 23 62 60 Japan +81 45 453 9100 Russia/CIS +43 1 333 50 34 0
Australia +61 3 9757 4300 Europe-Other +43 1 333 50 34 0 Korea +82 2 3420 8600 Singapore +65 6289 1190
Austria +43 810 282 206 Finland +358 9 3291 0200 Latin America +1 561 688 8700 Spain +34 914 845 965
Belgium +32 53 73 42 41 France +33 1 60 92 48 00 Middle East +43 1 333 50 34 0 Sweden +46 8 556 468 00
Canada +1 800 530 8447 Germany +49 6103 408 1014 Netherlands +31 76 579 55 55 Switzerland +41 61 716 77 00
China 800 810 5118 (free call domestic) India +91 22 6742 9494 New Zealand +64 9 980 6700 UK +44 1442 233555
400 650 5118 Italy +39 02 950 591 Norway +46 8 556 468 00 USA +1 800 532 4752
AN42218-EN 01/15S